CN106984259A - Polynary high-activity component absorbent for carbon monooxide and preparation method and application - Google Patents

Polynary high-activity component absorbent for carbon monooxide and preparation method and application Download PDF

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CN106984259A
CN106984259A CN201710316221.3A CN201710316221A CN106984259A CN 106984259 A CN106984259 A CN 106984259A CN 201710316221 A CN201710316221 A CN 201710316221A CN 106984259 A CN106984259 A CN 106984259A
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active component
component
absorbent
activity
presoma
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CN106984259B (en
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缪廷春
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Dalian New Material Environmental Protection Co St
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Dalian New Material Environmental Protection Co St
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Abstract

The present invention relates to polynary high-activity component absorbent for carbon monooxide and preparation method and application.The polynary high activity removal of carbon monoxide adsorbent of the present invention, is mainly made up, active component includes Cu, Zn, Mn, Ni, Fe high oxide of active component coprecipitation：CuO、ZnO、MnOx、NiO、FeOy, dispersant A l2O3Powder.The characteristics of present invention is using different component performance complement, by oxidation, makes multicomponent mixture reach high-valence state, and then realize the ability of chemisorbed removal of carbon monoxide.Its effect of the catalyst of the present invention is better than one-component or the catalyst of bi-component, there is not lose unstripped gas active principle, removing depth is high, capacity is big, activation temperature is low, anti-caking power strong, service life length, high mechanical strength, be not pulverized easily, and the absorbent for carbon monooxide is applied to C2H4、C3H6、CH4、H2、N2, He, Ne, Ar, Kr, Xe and electron gas deeply removing CO, can be widely applied to large-scale industrial production.

Description

Polynary high-activity component absorbent for carbon monooxide and preparation method and application
Technical field
The present invention relates to the suction of the carbon monoxide applied to industries such as petrochemical industry, electronics, metallurgy, gas, analysis, semiconductors Attached dose and preparation method and application, particularly a kind of multicomponent reactive component absorbent for carbon monooxide and preparation method thereof is with answering With.
Background technology
The carbon monoxide scavenger that presently relevant patent document is related to is divided into two major classes：The first kind be catalytic reaction type such as Pd/Al2O3Deng, its removal mechanism be precious metals pd as catalyst, the oxygen contained using raw material itself or by with oxygen Removing purpose is reached with reaction of carbon monoxide generation carbon dioxide in raw material.But there is following ask in such carbon monoxide scavenger Topic：First, because catalyst contains precious metals pd in itself, in removing hydrocarbon in carbon monoxide process, alkene is easily made to occur polymerisation Green oil is produced, brings new impurity to pollute；2nd, it is difficult to control to amount of oxygen during oxygen, makes to introduce new impurity oxygen in raw material Gas causes carbon monoxide removing depth not high with oxygen amount deficiency.
Equations of The Second Kind is chemisorbed scavenger, such as Cu, Zn system, and its removal mechanism is：Utilize the oxidizing gas such as oxygen The metal oxide of lower valency into high-valence state, it is anti-that oxidationreduction occurs for the metal oxide and carbon monoxide of high-valence state Should, and then reach the purpose of removal of carbon monoxide.Its chemisorbed removal of carbon monoxide of such scavenger it is limited in one's ability, at one section Between after, when high-valence state metal oxide is converted to lower valency oxide entirely, adsorbent is no longer with removal of carbon monoxide Ability, now, need to be passed through oxygen, air or other oxidizing gas and carry out regeneration activating.The chemisorbed scavenger is applied to Carbon monoxide content is less than the technique that 500ppm, particularly carbon monoxide content are less than 200ppm, such carbon monoxide in raw material There is small capacity, removing depth difference in scavenger, mechanical strength is low, too high easy-sintering of local temperature etc. when using in use Technical problem.
Compared to noble metal catalyst, the active high, reaction temperature of catalyst of the base metal type such as cupric oxide it is low and Lower-price characteristic, so to the linguistic term of this catalyst widely in recent years.In past ten several years, largely Cupric oxide is all recorded in document and is mixed with other metal oxides all good catalytic activity to low-temperature oxidation carbon monoxide, Air pollution treatment, treating vehicle exhaust and to fuel cell reaction gas purify in terms of all have a good application prospect.This CuO/ZnO absorbent for carbon monooxide prepared by invention coprecipitation method can be compared with carbon monoxide oxidation under low ambient temperature. Shown in research, Mn, Ni, Fe not only can be with adsorption reaction carbon monoxide, while between can strengthening multicomponent mixture as auxiliary element Interaction, improves the reactivity of catalyst.
The content of the invention
The present invention to solve in the prior art, absorbent for carbon monooxide has a removing, and capacity is small, removal of carbon monoxide depth not It is high, there is provided a kind of polynary high-activity component absorbent for carbon monooxide the problem of service life is short.
The inventive concept of the present invention is such：Although active component Cu or Zn itself has certain removal of carbon monoxide Ability, but individually one or two kinds of have that unavoidable removal of carbon monoxide depth is low, removing capacity is small, anti-unstripped gas is miscellaneous Matter carbon monoxide content fluctuation ability, the easily inferior position such as sintering, short life.The present invention utilizes the spy of different component performance complement Point, reaches high-valence state by aoxidizing multicomponent and realizes ability that multicomponent reactive component has chemisorbed removal of carbon monoxide.This The absorbent for carbon monooxide of invention, which has, does not lose that unstripped gas active principle, removing depth are high, capacity is big, anti-unstripped gas impurity one The advantages of content of carbon oxide fluctuation ability is strong, temperature in use is low, anti-caking power is strong, service life is long, can be widely applied to big Technical scale metaplasia is produced.
The preparation that the absorbent for carbon monooxide passes through co-precipitation by five kinds of active components Cu, Zn, Mn, Ni, Fe presoma Method is synthesized.Five yuan of high-activity component catalyst of the present invention, five kinds of active component performance complements.
The invention is characterized in that：Polynary high-activity component absorbent for carbon monooxide, is mainly co-precipitated by active component Method is made, and active component includes Cu, Zn, Mn, Ni, Fe high oxide：CuO、ZnO、MnOx、NiO、FeOy, dispersant Al2O3Powder, wherein x=1~2, y=1~1.5.
Further, in active component, active element Cu, Zn, Mn, Ni, Fe account for respectively catalyst gross mass 15~ 30%th, 15~30%, 0.05~2%, 0.05~2%, 0.05~2%.
Further, the dispersant A l2O3Powder accounts for the 30~45% of absorbent for carbon monooxide gross mass.
Further, the presoma of the active component CuO is：CuCO3Or Cu (NO3)2In one kind；The activearm Point ZnO presoma is：ZnCO3Or Zn (NO3)2；The active component MnOxPresoma be：MnCO3Or Mn (NO3)2.It is described Active component NiO presoma is：NiCO3Or Ni (NO3)2.The active component FeOyPresoma be：Fe(NO3)3.As A preferred embodiment of the invention, active component presoma is respectively Cu (NO3)2、Zn(NO3)2、Mn(NO3)2、Ni(NO3)2、 Fe(NO3)3。
Another object of the present invention is that the preparation side of above-mentioned polynary high-activity component absorbent for carbon monooxide is claimed Method, comprises the following steps:
(1) mixture of active component presoma is mixed in 50-80 DEG C of dissolving；To reach more preferable effect, the step Suddenly (1) is first to dissolve active component Cu, Zn presoma to mix, then Mn, Ni, Fe are dissolved into mixing.
(2) mixed solution obtained by step (1) is added into reactor, be sufficiently stirred for, and be heated to 60-80 DEG C.
(3) by excessive 20% Na2CO3Reactor is injected after dissolving, more specifically：Dissolve Na2CO3In 60-80 DEG C of water In, 1-2h time is fully injected into progress ageing reaction in reactor.
(4) the pH value control of ageing reactant mixture is in 9-10, and 60-80 DEG C of ageing reaction temperature control, time control exist 2-6h。
(5) step (4) is aged to the mixed liquor after reaction terminates and moisture is centrifuged, obtained filter cake, filter cake is broken up And in 60-80 DEG C of washing of warm water, operate 2-3 times repeatedly, until pH value is between 6-7.
(6) by the filter cake after step (5) processing, dehumidify and in 550-750 DEG C of roasting 3-7h of high temperature, obtain activating oxide Powder.
(7) activity powder after step (6) is calcined granulates tabletting, obtains polynary high-activity component absorbent for carbon monooxide.
3rd purpose of the invention is that above-mentioned polynary high-activity component absorbent for carbon monooxide is claimed in C2H4、 C3H6、CH4、H2、N2, application in He, Ne, Ar, Kr, Xe and electron gas depth removal of carbon monoxide.
The removal of carbon monoxide mechanism of the polynary high-activity component adsorbent of the present invention is as follows：
AOx+nCO——AOx-n+nCO2+Q
The regeneration mechanism of the polynary high-activity component catalyst of the present invention is as follows：
AOx-2n+nO2——AOx+Q
Compared with prior art, the beneficial effects of the invention are as follows：The characteristics of present invention is using different component performance complement, leads to Reduction multicomponent is crossed to reach high-valence state to realize ability that multicomponent reactive component has chemisorbed removal of carbon monoxide.The present invention's Catalyst its effect better than one-component or the catalyst of bi-component, with do not lose unstripped gas active principle, removing depth it is high, The advantages of capacity is big, activation temperature is low, anti-caking power strong, service life length, high mechanical strength are not pulverized easily, and an oxygen Change carbon adsorbent and be applied to C2H4、C3H6、CH4、H2、N2, He, Ne, Ar, Kr, Xe and electron gas depth removal of carbon monoxide, can be extensive Applied to large-scale industrial production.
Embodiment
The present invention is described in detail below by instantiation, but not limited the scope of the invention.Unless otherwise specified, this hair Bright used experimental method is conventional method, and experiment equipment used, material, reagent etc. chemically company can be bought.
Embodiment 1
Cu (NO are weighed in proportion3)2、Zn(NO3)2、Mn(NO3)2、Ni(NO3)2、Fe(NO3)3, proportioning is as shown in table 1, Several material stirring and dissolvings in 65 DEG C of hot water, mixed liquor is injected in reactor above, the maturing agent of configuration excessive 20% Na2CO3Solution, is slowly injected into same reactor and carries out 4h ageing reactions, and then reaction controlling will in 70 DEG C, pH value 9-10 Reacted slurry carries out centrifugation filter cake processed, breaks up washing (70 DEG C of water temperature) repeatedly 2-3 times, to slurry pH value 6-7, then by filter cake Low temperature drying and 600 DEG C of high-temperature roasting 5h, are a granulated into column type Ф 5 × (3~7) standby by the activating oxide powder Jing Guo high-temperature roasting With.Take 200ml catalyst to be fitted into Ф 40mm × 2.5mm × 300mm stainless steel reactor respectively, be passed through nitrogen air speed 10h-1 Purge 2h.Under the conditions of pressure 0.5MPa, 80 DEG C of temperature, ethene, ethene gas phase air speed 4000h are passed through-1, entrance carbon monoxide contains Measure removal of carbon monoxide capacity under the conditions of 100ppm, removal of carbon monoxide depth≤1ppm is measured, 1 is the results are shown in Table.
Embodiment 2~6
Preparation method and method of testing be the same as Example 1, the composition for differing only in adsorbent are different, specifically refer to table 1.
The composition and evaluation result of the embodiment 1-6 absorbent for carbon monooxide of table 1
Embodiment 7
Cu (NO are weighed in proportion3)2、Zn(NO3)2、Mn(NO3)2、Ni(NO3)2、Fe(NO3)3, proportioning is as shown in table 1, Several material stirring and dissolvings in 65 DEG C of hot water, mixed liquor is injected in reactor above, the maturing agent of configuration excessive 20% Na2CO3Solution, is slowly injected into same reactor and carries out 4h ageing reactions, and then reaction controlling will in 70 DEG C, pH value 9-10 Reacted slurry carries out centrifugation filter cake processed, breaks up washing (70 DEG C of water temperature) repeatedly 2-3 times, to slurry pH value 6-7, then by filter cake Low temperature drying and 600 DEG C of high-temperature roasting 5h, are a granulated into column type Ф 5 × (3~7) standby by the activating oxide powder Jing Guo high-temperature roasting With.Take 200ml catalyst to be fitted into Ф 40mm × 2.5mm × 300mm stainless steel reactor respectively, be passed through nitrogen air speed 10h-1 Purge 2h.Under the conditions of pressure 0.5MPa, 90 DEG C of temperature, ethene, ethene gas phase air speed 4000h are passed through-1, entrance carbon monoxide contains 100ppm is measured, removal of carbon monoxide depth≤0.02ppm determines removal of carbon monoxide capacity for 25.2ml/g.
Embodiment 8
Cu (NO are weighed in proportion3)2、Zn(NO3)2、Mn(NO3)2、Ni(NO3)2、Fe(NO3)3, proportioning is as shown in table 1, Several material stirring and dissolvings in 50-80 DEG C of hot water, mixed liquor is injected in reactor above, the maturing agent of configuration excessive 20% Na2CO3Solution, be slowly injected into same reactor carry out 2-6h ageing reaction, reaction controlling in 60-80 DEG C, pH value 9-10, Then reacted slurry is carried out centrifuging filter cake processed, breaks up washing (50-80 DEG C of water temperature) and repeat 2-3 times, to slurry pH value 6- 7, then by filter cake low temperature drying and 550-750 DEG C of high-temperature roasting 3-7h, the activating oxide powder Jing Guo high-temperature roasting is a granulated into Column type Ф 5 × (3~7) are standby.The stainless steel reactor for taking 200ml catalyst to load Ф 40mm × 2.5mm × 300mm respectively In, it is passed through nitrogen air speed 10h-1Purge 2h.Under the conditions of pressure 0.5MPa, 90 DEG C of temperature, ethene, ethene gas phase air speed are passed through 4000h-1, entrance carbon monoxide content 200ppm determines capacity under the conditions of removal of carbon monoxide depth≤1ppm, the results are shown in Table 2.
Embodiment 9~11
Composition, preparation method and the method for testing be the same as Example 1 of catalyst, differ only in sintering temperature difference, specifically Refer to table 2.
The embodiment 9-12 catalyst sintering temperature of table 2 and evaluation result
Embodiment 12
Catalyst is obtained with the composition and preparation method of the catalyst of embodiment 4, absorbent for carbon monooxide 150kg is weighed, used In nitrogen removal of carbon monoxide.
(1) ratio of height to diameter of bed is loaded：L/ Ф=8
(2) loadings：150kg
(3) nitrogen treatment amount：100Nm3/h
(4) carbon monoxide content 20ppm in nitrogen
(5) temperature in use：50-100℃
(6) product nitrogen gas is introduced without new impurity, and lossless
(7) removal of carbon monoxide depth：≤0.01ppm
(8) removal of carbon monoxide capacity：24.6ml/g
Embodiment 13
Catalyst is obtained with the composition and preparation method of the deoxidier of embodiment 6, absorbent for carbon monooxide 1.8kg is weighed, used In helium removal of carbon monoxide.
(1) ratio of height to diameter of bed is loaded：L/ Ф=11.48
(2) loadings：1.8kg
(3) helium treating capacity 1Nm3/h
(4) carbon monoxide content 5ppm in helium
(5) temperature in use：50-100℃
(6) product helium is introduced without new impurity, and lossless
(7) depth：≤0.01ppm
(8) capacity：21.3ml/g
The foregoing is only a preferred embodiment of the present invention, but protection scope of the present invention be not limited thereto, Any one skilled in the art in the technical scope of present disclosure, technique according to the invention scheme and its Inventive concept is subject to equivalent substitution or change, should all be included within the scope of the present invention.

Claims (7)

1. many yuan of high-activity component absorbent for carbon monooxide, it is characterised in that be mainly made up of active component coprecipitation, activity Component includes Cu, Zn, Mn, Ni, Fe high oxide：CuO、ZnO、MnOx、NiO、FeOy, dispersant A l2O3Powder, wherein x= 1~2, y=1~1.5；In active component, active element Cu, Zn, Mn, Ni, Fe account for respectively catalyst gross mass 15~30%, 15~30%, 0.05~2%, 0.05~2%, 0.05~2%.
2. polynary high-activity component absorbent for carbon monooxide according to claim 1, it is characterised in that active component CuO Presoma be：CuCO3Or Cu (NO3)2In one kind；The presoma of the active component ZnO is：ZnCO3Or Zn (NO3)2；Institute State active component MnOxPresoma be：MnCO3Or Mn (NO3)2；The presoma of the active component NiO is：NiCO3Or Ni (NO3)2；The active component FeOyPresoma be：Fe(NO3)3。
3. polynary high-activity component absorbent for carbon monooxide according to claim 1, it is characterised in that active component forerunner Body is respectively Cu (NO3)2、Zn(NO3)2、Mn(NO3)2、Ni(NO3)2、Fe(NO3)3。
4. a kind of preparation method of polynary high-activity component absorbent for carbon monooxide as claimed in claim 1, including following step Suddenly：
(1) mixture of active component presoma is mixed in 50-80 DEG C of dissolving；
(2) mixed solution obtained by step (1) is added into reactor, be sufficiently stirred for, and be heated to 60-80 DEG C；
(3) by a certain amount of Na2CO3Reactor is injected after dissolving and carries out ageing reaction；
(4) pH=9-10 of reactant mixture, 60-80 DEG C of reaction temperature of ageing, time 2-6h are aged；
(5) by step (4) be aged reaction terminate after mixed liquor moisture is centrifuged, obtain filter cake, by filter cake break up and in 60-80 DEG C of washing of warm water, is operated 2-3 times, until pH=6-7 repeatedly；
(6) by the filter cake after step (5) processing, dehumidify and in 550-750 DEG C of roasting 3-7h of high temperature, obtain activating oxide powder；
(7) activity powder after step (6) is calcined granulates tabletting, obtains polynary high-activity component absorbent for carbon monooxide.
5. preparation method according to claim 4, it is characterised in that the step (1) is first by before active component Cu, Zn Body dissolving mixing is driven, then Mn, Ni, Fe are dissolved into mixing.
6. preparation method according to claim 4, it is characterised in that the step (3) is specially：By Na2CO3It is dissolved in In 60-80 DEG C of water, 1-2h time is fully injected into progress ageing reaction in reactor.
7. a kind of polynary high-activity component absorbent for carbon monooxide as claimed in claim 1 is in C2H4、C3H6、CH4、H2、N2、He、 Application in Ne, Ar, Kr, Xe and electron gas depth removal of carbon monoxide.
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